USE OF MAGNETIC MESOPOROUS POLY(IONIC LIQUID) INTERFACIAL CATALYST IN HYDROGENATION REACTION AND PREPARATION OF BIODIESEL

Abstract

The disclosure provides use of an efficient, recyclable, green and friendly catalyst to realize a method of hydrogenation of an unsaturated alkene, and a method for preparing biodiesel through the transesterification of soybean oil with ethanol. The method of hydrogenation of the unsaturated alkene comprises performing a hydrogenation reaction of an unsaturated alkene at ambient temperature and atmospheric pressure by using a CO.sub.2 and magnetic dual-responsive mesoporous poly(ionic liquid) as a catalyst I, and using n-hexane and water as a solvent, to obtain a corresponding saturated alkane. The method for preparing biodiesel through transesterification of soybean oil with ethanol comprises performing a transesterification reaction of soybean oil with ethanol at a temperature of 25-90° C. and atmospheric pressure by using a CO.sub.2 and magnetic dual-responsive mesoporous poly(ionic liquid) as a catalyst II, to obtain the biodiesel.

Claims

1. A method of hydrogenation of an unsaturated alkene, comprising: performing a hydrogenation reaction of an unsaturated alkene at ambient temperature and atmospheric pressure by using a CO.sub.2 and magnetic dual-responsive mesoporous poly(ionic liquid) as a catalyst I, and using n-hexane and water as a solvent, to obtain a corresponding saturated alkane.

2. The method of claim 1, wherein the catalyst I has a large specific surface area of 51.22-272.49 m.sup.2.Math.g.sup.-1 and a good pore size distribution, and is prepared by a template-free process comprising introducing 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TEMPA) monomer and a terminal alkene-modified Fe.sub.3O.sub.4@SiO.sub.2.

3. The method of claim 1, wherein a volume ratio of n-hexane to water is 1:1, 1:2, or 2:1.

4. The method of claim 1, wherein a molar ratio of the catalyst I to the unsaturated alkene is in a range of 0.007: 1 to 0.012: 1.

5. The method of claim 1, wherein the hydrogenation reaction by using the catalyst I is performed at ambient temperature and atmospheric pressure.

6. The method of claim 1, wherein the unsaturated alkene is selected from a group consisting of styrene, phenylacetylene, allylbenzene, cyclohexene, n-butyl acrylate, butyl methacrylate, 1-octene, and 1-dodecene.

7. The method of claim 1, further comprising: after the hydrogenation reaction, separating the catalyst I from a first product solution by an external magnetic force and blowing CO.sub.2, and pouring out a first clear liquid from the first product solution to obtain a first product; and washing the catalyst I with methanol to obtain a washed catalyst I, and vacuumdrying the washed catalyst I at 60° C. for 5 hours, such that the catalyst I is recyclable for more than one time.

8. The method of claim 2, wherein the unsaturated alkene is selected from a group consisting of styrene, phenylacetylene, allylbenzene, cyclohexene, n-butyl acrylate, butyl methacrylate, 1-octene, and 1-dodecene.

9. The method of claim 3, wherein the unsaturated alkene is selected from a group consisting of styrene, phenylacetylene, allylbenzene, cyclohexene, n-butyl acrylate, butyl methacrylate, 1-octene, and 1-dodecene.

10. The method of claim 4, wherein the unsaturated alkene is selected from a group consisting of styrene, phenylacetylene, allylbenzene, cyclohexene, n-butyl acrylate, butyl methacrylate, 1-octene, and 1-dodecene.

11. A method for preparing biodiesel through transesterification of soybean oil with ethanol, comprising: performing a transesterification reaction of soybean oil with ethanol at a temperature of 25-90° C. and atmospheric pressure by using a CO.sub.2 and magnetic dual-responsive mesoporous poly(ionic liquid) as a catalyst II, to obtain the biodiesel.

12. The method of claim 11, wherein the catalyst II has a large specific surface area of 51.22-272.49 m.sup.2.Math.g.sup.-1 and a good pore size distribution, and is prepared by a template-free process comprising introducing 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TEMPA) monomer and a terminal alkene-modified Fe.sub.3O.sub.4@SiO.sub.2.

13. The method of claim 11, wherein a molar ratio of ethanol to soybean oil is in a range of 5:1 to 19:1.

14. The method of claim 11, wherein the transesterification reaction by using the catalyst II is performed at a temperature of 25-90° C.

15. The method of claim 11, wherein a molar ratio of the catalyst II to soybean oil is in a range of 0.007: 1 to 0.035:1.

16. The method of claim 11, further comprising: after the transesterification reaction, separating the catalyst II from a second product solution by an external magnetic force and blowing CO.sub.2, and pouring out a second clear liquid from the second product solution to obtain a second product; and washing the catalyst II with methanol to obtain a washed catalyst II, and vacuumdrying the washed catalyst II at 60° C. for 5 hours, such that the catalyst II is recyclable for more than one time.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings, which are incorporated in and constitute a part of this description, illustrate embodiments consistent with the present disclosure, and together with the description serve to explain the principles of the present disclosure.

[0029] FIG. 1 shows a flow chart of the preparation of the magnetic mesoporous poly(ionic liquid) interfacial catalyst in one embodiment of the present disclosure;

[0030] FIG. 2 shows the molecular formula of the ionic liquid monomer in one embodiment of the present disclosure;

[0031] FIG. 3 shows a schematic structure of the catalyst Pd-p(xTEMPA-yFDABCO-zDVB)@Fe.sub.3O.sub.4 in one embodiment of the present disclosure; and

[0032] FIG. 4 shows a schematic structure of the catalyst p(xTEMPA-y[FDABCO][OH]-zDVB)@Fe.sub.3O.sub.4 in one embodiment of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] The present disclosure will be further described below in conjunction with examples. The examples of the present disclosure are only used to illustrate the technical solutions of the present disclosure and are not intended to limit the present disclosure.

Example 1

[0034] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), styrene (2 mmol), n-hexane (1 mL), and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 99%.

Example 2

[0035] Pd-p(TEMPA-FDABCO-DVB)@Fe.sub.3O.sub.4 (20 mg), styrene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 60.59%.

Example 3

[0036] Pd-p(2.5TEMPA-2.5FDABCO-DVB)@Fe.sub.3O.sub.4 (20 mg), styrene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 54.72%.

Example 4

[0037] Pd-p(TEMPA-3FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), styrene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 80.77%.

Example 5

[0038] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (15 mg), styrene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 71%.

Example 6

[0039] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), phenylacetylene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 15 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 91%.

Example 7

[0040] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), allylbenzene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 99%.

Example 8

[0041] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), cyclohexene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 20 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 88%.

Example 9

[0042] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), n-butyl acrylate (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as the final product, with a conversion of 99%.

Example 10

[0043] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), butyl methacrylate (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as a final product, with a conversion of 99%.

Example 11

[0044] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), 1-octene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 15 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as a final product, with a conversion of 99%.

Example 12

[0045] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), 1-dodecene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 20 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as a final product, with a conversion of 99%.

Example 13

[0046] Pd-p(3TEMPA-FDABCO-2DVB)@Fe.sub.3O.sub.4 (20 mg), styrene (2 mmol), n-hexane (1 mL) and water (2 mL) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. H.sub.2 was then circulated into the Pickering emulsion and reacted for 10 min. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid from the product solution was collected as a final product, with a conversion of 99%. The catalyst was recycled for 5 times, without significant decrease in yield, as shown in Table 1.

Example 14

[0047] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution is subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 80.84%.

Example 15

[0048] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 25° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution is subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 75.87%.

Example 16

[0049] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion is subjected to a reaction at 90° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 91.55%.

Example 17

[0050] p(TEMPA-[FDABCO][OH]-4DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 41.45%.

Example 18

[0051] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (5 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 47.91%.

Example 19

[0052] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (10 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 79.42%.

Example 20

[0053] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (19 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 65.43%.

Example 21

[0054] p(3TEMPA-[FDABCO][OH]-2DVB)@Fe.sub.3O.sub.4 (20 mg), soybean oil (1.145 mmol), and ethanol (10 mmol) were added into a reaction tube, and intensely stirred to form a stable Pickering emulsion. The Pickering emulsion was subjected to a reaction at 65° C. and atmospheric pressure for 4 h. The reaction was monitored by gas chromatography. After the reaction, the catalyst was separated from a product solution by an external magnetic force and CO.sub.2, and a clear liquid of the product solution was subjected to an extraction with n-hexane, obtaining biodiesel, with a yield of 80.84%. The catalyst was recycled for 5 times, without significant decrease in yield, as shown in Table 2.

TABLE-US-00001 Times Temperature (°C) Time for reaction (min) Conversions(%) 1 25 10 99 2 25 10 97 3 25 10 93 4 25 10 94 5 25 10 90

TABLE-US-00002 Times Temperature (°C) Time for reaction (h) Yield(%) 1 65 4 80.84 2 65 4 80.34 3 65 4 78.67 4 65 4 76.37 5 65 4 50.23

[0055] It should be noted that the above summary and the specific embodiments of the present disclosure are intended to prove the practical application of the technical solutions according to the present disclosure and should not be construed as limiting the scope of the present disclosure. Those skilled in the art could make various modifications, equivalent substitutions, or improvements within the spirit and principles of the present disclosure. The scope of the present disclosure is accorded with the appended claims.